Fungicidal method and composition involving polymeric thiadiazinethione compounds



United States Patent FUNGICIDAL METHOD AND COMPOSITION IN- VOLVING POLYMERI TPHADIAZENETHIONE COMPOUNDS Earl W. Cummins, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del, a corporation of Delaware N0 Drawing. Uriginal application May 2, 1960, Ser. No. 25,856, new Patent No. 3,126,378, dated Mar. 24, 1964. Divided and this application Dec. 6, 1963, Ser. No.

2 Claims. c1. ran-33 R is alkyl or alkenyl of (C C R and R are same or different from group consisting of alkylene of 2-6 carbon atoms; R is hydrogen and alkyl or alkenyl (C -C and n is a positive whole number.

The stable polymeric thiadiazinethiones and compositions of this invention are effective agents for the protection of organic matter subject to fungus infection as for example prevention of apple scab and tomato blight. Generally, the crude reaction products contain substantial amounts of the polymeric thiadiazinethiones of this invention and are adequate for direct formulation and use as fungicide agents without further purification.

A convenient method for the preparation of the novel polymeric thiadiazinethiones follows: Generally the method involves the addition of an aqueous or aqueousalcoholic solution of an alkylene diamine or a mixture of alkyl amines and alkylene diamines to an aqueousalcoholic solution of an alkylenebisdithiocarbamic acid or a mixture of mono and bisdithiocarbamic acids, followed by the immediate addition of an aqueous aldehyde solution. The reaction is generally completed in about 1 to 2 hours under normal atmospheric conditions. The solid reaction mixtures containing substantial quantities of the polymeric thiadiazinethiones of this invention are then removed by filtration, washed with water and dried.

The degree of polymerization can be controlled by varying the ratio of the difunctional reactants (alkylene diamine, alkylenebisdithiocarbamic acids and aldehyde) to the monofunctional reactants (alkyldithiocarbamic acid and/or alkyl amine). The type'of polymer obtained is defined by the monofunctional reactants (i.e., the chain terminating reactants) used.

The chain terminating reactants are generally mixed with the alkylene diamine and the alkylenebisdithiocarbamic acid before the addition of the aldehyde. However, in some instances, the addition of the chain terminating reactants may be made simultaneously with the aldehyde throughout the course of the reaction. Unstable long-chain polymeric solids result unless the chain terminating reactants are added at least partially to the chain promoting reactants at the beginning of the reaction; prior to solid precipitation from the reaction medium.

The following subgeneric structures for the thiadiazinethiones of this invention illustrate generally that the polymerization can proceed and can be terminated or capped at both ends in three ways by the appropriate use of the monofunctional and difunctional reactants mentioned above.

(a) Alkyl amine moiety at both ends. (b) H-alkyl dithiocarbamic acid moiety at both ends. (c) Combination of a and b above.

1 ALKYL N AT BOTH ENDS [I II S S CAPPED AT BOTH ENDS WITH MONOALKYLDI- THIOCARBAMYL MOIETY (III) CAPPED WITH ALKYL AMINE AND ALKYL DITHIOCARBAMYL MOIETIES These structures further illustrate that the thiadiazinethiones of this invention are linked by alkylene groups via their amino and thio amido nitrogens. The ratio of amino alkylene groups to thio amido alkylene groups in a given polymeric product is controlled by the molar ratios of the difunctional reactants used in the reaction. For example, the three types of polymeric thiodiazinethiones of this invention illustrated by formulae II, III, IV above are prepared by reacting the ratios of molar equivalents of the reactants given in Table I below:

Note than n of Formulae II, III, and IV above which defines the extent of polymerization and the n times the molar equivalents of the reactants listed in Table I are interrelated and numerically the same. For example when n=3 in Table I, the corresponding polymeric thiadiazinethione II, III, or IV containing 3 repeating units (n=3) are formed in substantial quantities.

The conditions of the reactions, for example, the exact temperature employed, the amount and type of solvent for the reactants, the rate of addition of the aldehyde, the concentration of the reactant solutions etc., will be dependent on the reactants employed and the extent of polymerization desired.

The fungicidal polymeric thiodiazineth'iones of this invention are in general White solids having melting points in the range of 60 20 C. They are essentially insolutale in water and alcohols.

In practicing the fungicidal methods of my invention, one or more of the active ingredients is applied to the organic material to be treated for the control of fungi at a dosage sufficient to exert fungicidal action. Accordingly, my compositions and methods are applicable for the protection of carbohydrates, proteins and fats. They are particularly suited for the treating of living plant life such as vegetables, ornamental plants and fruit-bearing trees. Also they can be used to treat organic fibers and fabrics, leather and various cellulosic materials such as wood. Likewise they can be used to treat paints and lubricating oils.

In application to plants, fungicidal control is obtained in most instances by applying the active compound at a dosage or rate from about 1 to 10 pounds per acre, the optimum amount within this range being largely dependent upon the variables mentioned hereafter. It is, of course, determined by and dependent upon the particular fungicidal compound selected, the method of application, and, in the case of application to vegetation, the state and condition of growth of the vegetation to be treated, and the climatic conditions.

The fungicidal compositions of my invention contain in sufficient amount to exert fungicidal action one or more of the above-described active compounds in admixture with a carrier material or conditioning agent of the kind used and commonly referred to in the art as a fungicide adjuvant or modifier. The conventional fungicideadjuvants are inert solids, hydrocarbon liquid diluents and surface-active agents. They provide formulations adapted for ready and efiicient application using conventional applicator equipment. Usually from about 1 to 95% by weight of the fungicidal composition is active ingredient.

Solid compositions are preferably in the form of powders. They are compounded to be homogeneous powders that can be either used as such, diluted with inert solids to form dusts, or suspended in a suitable liquid medium for spray application. The powders usually comprise active ingredient admixed With minor amounts of conditioning agent. Natural clays, either adsorptive such as attapulgite or relative non-absorptive such as kaolin clays, diatomaceous earth, walnut shell flour, tobacco dust, redwood flour, synthetic fine silica, calcium silicate and other inert solid carriers of the kind conventionally employed in powder fungicidal compositions can be used. The active ingredient usually makes up from about 25 to of these powder compositions. For conversion of the powders to dusts, talc, pyrophyllite, tobacco dust, volcanic ash and other dense, rapid-settling inert solids customarily are used.

Liquid compositions employing one or more of the fungicidally-active ingredients are prepared by admixing the active ingredient with a suitable liquid diluent medium. The active ingredient can be either in solution or in suspension in the liquid medium. Typically of the liquid media commonly employed as fungicide adjuvants are kerosene, Stoddard solvent, xylene, alcohols, alkylated naphthalene and glycols. The active ingredient usually makes up from about 0.5 to 50% of these liquid compositions. Some of these compositions are designed to be used as such, and others to be extended with large quantities of water.

Compositions in the form of wettable powders or liquids in many cases also include one or more surfaceactive agents such as wetting, dispersing or emulsifying agents. These materials cause the compositions to disperse or emulsify easily in water to give aqueous sprays.

The surface-active agents employed can be of the anionic, cationic or nonionic type. They include, for example, sodium oleate, sulfonated petroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates and other surface-active agents. A detailed list of such agents is set forth in an article by McCutcheon, entitled Synthetic Detergents and Emulsifiers, volume 31, 1955, of Soap and Chemical Specialties.

In some cases it may be desirable to employ the active compounds of the present invention in combination with other fungicides to give compositions that have broad spectrum fungicidal activity. In these mixtures, the fungicidally active materials can be present in any desired amount, ordinarily from about 0.1-20 parts by weight of a compound represented by Formula I per part by weight of the auxiliary fungicidally active material. In some instances it may even be desirable to employ two or more auxiliary fungicides.

5 Typical of the auxiliary fungicides that can be'employed in combination with the compounds of the present invention are the following:

6, tative yield of the stable, solid 5,5-[(tetrahydro-2-thiono- 2H 1,3,5 thiadiazin-3,5-ylene)diethylene]bis(tetrahydro-3-methyl-2H-1,3,S-thiadiazine-Z-thione) is isolated by filtration. After washing with water and drying, it-is adequate for formulation and fungicidal application without further purification.

Other polymeric thiadiazinethiones of this invention having the subgeneric structure IV shown above can be prepared similarly by substituting equivalent molar quantities of the reactants listed in Table II-belowforthe reactants of Example labove. Multiplesof the equivalent molar quantities of the difunctional reactants gives polymeric thiadiazinethiones of structure IV where n is greater than 1. For the purpose of clarity structural description of the products obtained are listed in Table II below rather than the language usedlto name the product obtained in Example 1 above.

TABLE II Reactauts Products obtained of subgeneric structure IV where R, R1, R R are Alkyl(Na+) Alkylenebis- Ex dl-HCl salt H01 salt of Aldehyde dithiocardithioear- Alkyl R R1 R R; n N0 of diamine amine bamie acid bamic acid 2Na+ salt 2 Ethylene Methyl- Ethyl Ethy1ene Methy1 H Ethylenenn Ethylene... -Ethy1 1 diamine. amine.

Isopropyl-.- do IsopropyL IsopropyL 1 Hexy1 do.-. H Hexyl 1 Laury1 d0 Lauryl 1 Methyl Ethyl H Methyl 1 Isobutyl do n-Buty1 Isobutyl 1 Ally do Allyl -Allyl 1 Octadecyl do Amyl Octadecyl. l dehyde Tert oety1 do Methy do Tert octyly 1 Allyl Propiono do Allyl d0 1 aldehyde Methyl Bitylragido do Methyl do 1 e e 13-.. Trimethdo Formgldo do do H d0 Propylene do 1 ylene. dehyde. 14--. Ethylene.-- n-Propyl Acrolein Tert. 0ctyl Hexamethyn-PropyL. Vmy. Hexameth- Ethylene.-- Tertt. 1 1

ene. y ene. 00 y 15 Hexameth- Methyl Crotonic Methyl do Methyl. Methyl d0 Hexameth- Methyl 1 ylene. vinyl. ylene. l6 Tetrameth- Lauryl Formal- Heptyl Pentarneth- Lauryl H Pentameth- Tetrameth- Heptyl 1 -ylene. ylene. ylene. ylene. 17 -Ethylene Methyl d Ethylene Methylufl H Ethylene Ethylene Methyl 2 18... ,do do o d0 do d0 3 19 do do o d0 do do 4 20--- Trimeth- Tert. Trimeth- Tert. Propylun Trimeth- Trimethn-Butyl 7 ylene. butyl. butyl. ylene. ylene. 21 -Ethylene--- Methyl Formal Methyl Ethylene Methyl H Ethylene-.. Ethylene MethyL..- 10

dehy e.

Manganese dimethyl 'dithiocarbamate plus Z-mercapto- Example 22 gi l -A solution of 135 pts. by wt. otmethylamine .hydro- Copper f fi fate chloride and 133 pts. by wt. of ethylenediamine dihydroi l ii mo ate chloride in 660 pts. by wt. of water was added rapidly to o exlim e arstirred solution of 512 pts. by wt. of ethylenebisdithioserramycm. carbamic acid disodium salt in 4000 pts. by wt. of water. treptomycm In rapid succession, 650 pts. by wt. of ,a 36.9% aqueous Compounds disclosed in my copending application Serial No. 809,597, filed April 29, 1959, now abandoned.

In order that the invention may be better understood, the following examples are given:

PREPARATIVE EXAMPLES Example .1

A solution containing 1500 pts. by wt. of water, 256 pts. by wt. of ethylenebisdithiocarbamic acid, disodium salt and 129 pts. by wt. of methyl dithiocarbamic acid,

sodiumsalt is added rapidly at room temperature to a formaldehyde solution was also added rapidly to the reaction. After a short induction period, solid precipitated. Continued stirring for two additional'hourscompleted the reaction. The solid was removed by filtration, washed was water and dried to give 527 pts. by wt. of 3,3-ethylleneb is[ (tetrahydro 2 thiono 2H 1,3,5 thiadiazin- 3,5 ylene) diethylene']'bis(tetrahydro 5 methyl 2H- 1,3,5-thiadiazine-2-thione), as a pale yellow solid, M.P.

Other polymeric thiadiazinethiones of this invention having the subgeneric structure II shown above can be prepared similarly by substituting equivalent molar quantities of the reactants listed in Table III'below for the reactants of Example 22 above. Multiples of the equivalent quantities of the difunctional reactants as shown in Table I gives the polymeric thiadiazinethiones of structure II where n is greater than one. For the purposes of clarity and understanding, structural identification of the prodwith water to give a 0.2% concentration of the active ucts obtained are listed in Table III below: ingredient. The resultant composition, when sprayed on TABLE III Reactants Products obtained of subgenerlc structure II where R, R1, R R3, are:

Allgylenebisdl- Ex. dl-HCl salt of HCl salt of the Aldehyde thlocarbamlc R R R; R; 11

No. diam ne amine acid, 2

2Na+salt 23 Ethylene Formaldehyde..- Ethylene Ethylene.-. Ethylene Ethyl 1 24 do do do rln rln All l 1 25 Aeetoldehydedo Butyl 1 26 Prlpponoldedo rln Hexyl 1 y e. 27 Trimethylene-.. Isopropyl Butyraldehyde Propy Trimethylene- Isopropyl. 1 28 Hexamethylene Lauryl Crotomc l,2-propylene-- MethylvinyL- 1,2-propylene Hexamethyl- Lauryl 1 ene. 29 1,2-butylene Methyl Butyraldehyde. Isobutylene--- Propyl Isobutylene 1,2-butylene..- Methyl 1 30 Ethylene Octadecyl Acrolein Hexamethyl- Vmyl Hexamethyl- Ethylene---" Ootadecyl 1 ene. ene. 31 Pentamethyl- Amyl Formaldehyde" Ethylene H Ethylene..-" Pentamethyl- 2 one. ene. 32 Ethylene Methyl do H Ethylene. 5 33 do do r H dn dn 6 34 do (in do dn Ff dn do 7 35 Tetramethylene- Heptyl Acetaldehyde-.- Trimethylene. H Trimethylene- Tetramethyl- 3 ene. 36 do Prepyl Pi gp i onalde- Ethylene..-" Ethyl Ethylene-.-" do Propyl 8 Example 37 tomato foliage, substantially prevents infection by early A solution of 266 pts. by wt. of ethylene diamine dihydrochloride contained in 600 pts. by wt. of water was added to a stirring aqueous solution of 256 pts. by wt. of ethylenebisdithiocarbamic acid, disodium salt and 258 pts. by wt. of N-methyldithiocarbamic acid, sodium salt in 4000 pts. by wt. of water, followed in rapid succession by the addition of 650 pts. by wt. of a 36.9% aqueous formaldehyde solution. Continued stirring of the reaction mixture at room temperature completed the reaction in two hours. The solid was removed by filtration washed with water. and dried to give 5,5'-ethylene bis[(tetrahydro 2 thione 2H 1,3,5 thiadiazin-3,5- ylene)diethylene]bis(tetrahydro 3 methyl 2H 1,3,5- thiadiazine-Z-thione).

Other polymeric thiadiazinethiones of this invention having the subgeneric structure III shown above can be prepared similarly by substituting equivalent molar quanblight (Alternaria solani) Percent 5,5-[(tetrahydro 2 thiono 2H 1,3,5 thiadiazin 3,5 ylene)diethylene]bis(tetrahydro 3- methyl 2H 1,3,5 thiadiazine 2 thiono) Sodium lauryl sulfate Sodium lignin sulfonate Kaolin clay Example 52 The following wettable powder when dispersed in water at a concentration of 2 pounds per 100 gallons of water and sprayed on tomato foliage at a rate of 100 gallons per acre, prevents early blight (Alternaria solani).

Percent 3,3 ethylenebis[(tetrahydro 2 thion0-2H-1,3,5- thiadiazin-3,5-ylene)diethylene]bistetrahydro 5- tities of the reactants listed in Table IV below for the methyl 2H 1,3,5 thiadiazine-Z-thione) 80.0 reactants of Example 37 above. Multiples'of the equiva- Alkylnaphthalene sulfonic acid solium salt 0.75 lent quantities of the difunctional reactants as shown in a Low viscosity methyl cellulose 0.25 Table I react to give the polymeric thiadiazine. Slhca 19.0

' TABLE IV Reactauts Products Obtained of Subgenerlc Structure III where R, R1, R1, R1

are:

Ex. di-HOl salt of Monodithio- Alkylenebisdi- No. diamine Aldehyde carbamic acid, thiocarbamie R R1 R; R, n

Na+ aeid, 2Na+ salt 38".-- Ethylene Formaldehyde" Ethyl Ethylene Fl Ethylene Ethylene 1 39 tdo Acetaldehyde... Propyl Tetramethyl- Metnyl Tetramethyldo 1 ene. ene.

Tetramethylene. Crotonic Ally Ethylene MethylvinyL. Ethylene Tetramethyll ene. Hexamethylene. Formaldehyde Methyl Hexamethyl- H Hexamethyl- Hexamethyl- 1 8118. ene. 8H6. Butyraldehyde" Laury Ethylene Propy Ethy Ethylene Laury 1 do Acrolein Methy Vinyl--- dn dn Methyl 1 Trimethylene. lsolbuityralde- Heptyl Isobntylene.-. Is0pr0pyl Isobutylene- Trimethylene- Heptyl 1 Ethylene Formaldehyde" Methyl Ethylene H Ethy Ethyl Methyl 10 d do do H do do dn 15 47 do do FT dn rln dn 22 48 do Acetaldehyde--. Buty Methyl --rln rln But l 5 49"-.. Pentamethyl- Propionalde- AmyL. Ethy -do Pentamethyl- Amyl 6 ene. hyde. ene. 50 Ethylene Formaldehyde. Decyl H rln Ethy Decyl 3 The following examples further illustrate the fungi- Example 53 cidal activity of the polymeric products of this invention:

Example 51 The following wettable powder composition is diluted A fungicidal dust composition of 5,5'-ethylenebis- [(tetrahydro-Z-thiono 2H 1,3,5-thiadiazin-3,5-ylene) diethylene]bis(tetrahydro-3-methyl 2H 1,3,5 thiadi- 9 azine 2 thione) is prepared. When dusted on bean plants at the rate of 10 pounds of active ingredient per acre, bean rust (Uromyces appendiculatus) is controlled.

Percent 5,5-ethylenebis[(tetrahydro 2 thiono- 2H 1,3,5-

thiadiazin 3,5 ylene)diethylene]bis(tetrahydro 3-methyl 2H 1,3,5 thiadiazine 2 thione) 20.0 Stearated calcium carbonate 80.0

Example 54 Poly 3,3 ethylenebis[(tetrahydro 2 thiono 2H- 1,3,5 thiadiazin 3,5 ylene)diethylene]bis(tetrahydro- 5 methyl 2H 1,3,5-thiadiazine 2 thione) is applied to tomato foliage as an aqueous dispersion at a concentration of 0 2%. When the spray deposit dries, the foliage is inoculated with the spores of the early blight fungus (Alternaria solani). After a suitable incubation time the leaves are examined for disease. It is found that the treated leaves have very little infection while the untreated control leaves have 100% disease.

The same compound is applied to bean plants as an aqueous suspension at a concentration of 0.008%. When the spray deposit has dried, the plants are exposed to infection by the spores of bean rust (Uromyees appendiculatus). After a suitable incubation period it is found that the treated plants have very little infection whereas the untreated control plants have 100% infection.

Example 55 This compound is formulated as a dust that is suitable for application by means of conventional dusting equipment by blending the active and minor diluents together and passing them through a micropulverizer, then blending the product with the major diluent in a ribbon blender.

Percent 5,5'-[(tetrahydro-2-thiono-2H 1,3,5-thiadiazin-3,5- ylene)diethylene]bis(tetrahydro 3 allyl 2H- 1,3,5-thiadiazine-2-thione) 25.0 Pyrophyllite 69.0 Attapulgite 6.0

This fungicidal composition, when dusted on tomato plants at a rate of 3 pounds per acre of active ingredient prevents infection by early blight (Alternaria solani).

Example 56 Example 41 previously cited is formulated as a fungicidal dust having the following composition:

Percent 5,5'-hexamethylenebis[(tetrahydro 2 thiono-ZH- 1,3,5-thiadiazin-3,5-ylene)dihexamethylene] bis tetrahydro-3-methyl-2H 1,3,5 thiadiazine-Z-thione) (Ex. 41) 20.0 Tobacco dust 80.0

This fungicidal dust is prepared by blending the listed ingredients and passing them through a micropulverizer. When the composition is dusted on pear trees at the rate of pounds per acre of actual ingredient, it is found to prevent pear scab (Venturia pyrina) Example 57 Percent Ex. 23 (named above) 80.0 Alkylnaphthalene sulfonic acid, sodium salt 0.75 Low viscosity methyl cellulose 0.25 Silica 19.0

10 Example 58' A wettable powder of the following composition is prepared.

5,5 (tetrahydro-Zdhiono-ZH-l ,3',5-thiadiazin 3,5- ylene)diethylene]bis(tetrahydro- 3 isopropyl-ZH- 1,3,5-thiadiazine-2-thione) 80.0 Alkylnaphthalene sulfonic acid, sodium salt 0.75 Low viscosity methyl cellulose 0.25 Diatomaceous earth 19.0

This wettable powder, when dispersed in water at a concentration of 2 pounds per gallons of water and sprayed on apple trees at the rate of 100 gallons per acre prevents infection by apple scab (Venturia inaequalis).

Octyl alcohol 0.005 Sodium lignin sulfonate 15.0 Hydrated attapulgite 1.75 Water 53.45

The above materials are mixed together and ground with suitable milling equipment, e.g., a pebble mill or sand mill, until the active material is substantially all below 5 microns in particle size. The resultant, stable, aqueous dispersion may then be diluted with water to suitable spray concentration. When sprayed on tomato foliage at the rate of 300 gallons per acre, early blight is prevented (A lternaria solani) I claim:

1. The method for the control of fungus attack of organic material comprising applying to the organic material to be protected a fungicidally effective amount of a compound of the formula R is selected from the group consisting of hydrogen, alkyl of 1 through 3 carbons, and alkenyl of 1 through 3 car- 11 12 bons; R and R are alkylene of 2 through 6 carbons; R References Cited by the Examiner is selected from the group consisting of hydrogen, alkyl UNITED STATES PATENTS of 1 through 18 carbons and alkenyl of 1 through 18 carbons; and n is a positive whole number. 3,085,046 4/1963 cummms 2. A- composition comprising a fungicidal amount of 5 a compound as defined in claim 1 and a major amount of JULIAN LEVITT Pnmary Examiner an inert solid particulate diluent. FRANK CACCIAPAGLIA, J 11., Examiner. 

1. THE METHOD FOR THE CONTROL OF FUNGUS ATTACK OF ORGANIC MATERIAL COMPRISING APLYING TO THE ORGANIC MATERIAL TO BE PROTECTED A FUNGICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA 